Crystal Structures of Hydrazinium(II) Salts of [SbF₆]^– and [Sb₂F₁₁]^–

Abstract

Abstract. N 2 H 6 (Sb 2 F 11 ) 2 was synthesized by the reaction of N 2 H 6 F 2 with excess of SbF 5 in anhydrous hydrogen fluoride (aHF). It crystallizes in the triclinic space group P1 (No. 2) with a = 6.6467(3) Å, b = 8.3039(4) Å, c = 8.3600(5) Å, α = 76.394 (5) o , β = 70.161 (5) o , γ = 70.797 (5) o , V = 405.90(4) Å 3 at 150 K, Z = 2. When it is redissolved in aHF, it solvolysis with the release of SbF 5 yielding N 2 H 6 (SbF 6 ) 2

Influence of the Increasing Size of the M2+ Cation on the Crystal Structures of XeF5M(SbF6)3 (M = Ni, Mg, Cu, Zn, Co, Mn, Pd) and (XeF5)3[Hg(HF)]2(SbF6)7

“…The M–F (M = Ni, Mg, Zn, Co, Mn) bond lengths (Table ) are comparable to those found in other M 2+ salts in which the M 2+ cations are located in an octahedral coordination of six fluorine atoms, for example, KNi(AsF 6 ) 3 and KM(AsF 6 ) 3 (M = Mg, Zn, Co, Mn). As expected, all the Sb–F bridging bonds are slightly elongated [1.892(4)–1.937(4) Å] in comparison with the Sb–F terminal bonds [1.831(4)–1.885(5) Å].…”

“…The three‐dimensional frameworks of [M(XF 6 ) 3 ] – (M = Ni, Cu, Fe, Zn, Co, Mn; X = As, Sb) constructed of rings of MF 6 octahedra that share apexes with XF 6 octahedra have already been shown to be a very common structural motif in many compounds. This arrangement leads to the formation of cavities within which various singly charged cations are located (H 3 O + , O 2 + , NO + , NH 4 + , K + , Rb, Cs + ) , , , . The latest example was the crystal structure of XeF 5 Cu(SbF 6 ) 3 , for which it was observed for the first time that even larger cations such as [XeF 5 ] + can be accommodated inside such cavities.…”

Synthesis and crystal structures of HgFAsF6, Hg(HF)2(AsF6)2, Hg(HF)(AsF6)2 and Hg(AsF6)(SO3F)

“…As in AgFAsF 6 [35] and CuFAsF 6 -types [37] the structure consists of zig-zag (M À F) n n þ (M¼ Hg) one dimensional chains interconnected by AsF 6 groups. Crystal structures of Hg(HF) 2 (AsF 6 ) 2 and Hg(HF)(AsF 6 ) 2 are new examples of compounds with HF directly bound to metal centre [28]. In the former, each Hg atom is found in an octahedral coordination of six fluorine atoms provided by two HF molecules and four AsF 6 units.…”

“…fluoride-ion acceptors [6,27]. However, their re-crystallizations from aHF solutions almost always yield M (HF) n (XF 6 ) 2 type of compounds with HF directly bound to the metal centres [28]. Since UV-visible spectra show that, in solutions of MF 2 in aHF acidified with Lewis acids (AsF 5 , BF 3 , etc.…”

“…Unfortunately, other suitable solvents as SO 2 , CH 3 CN, etc., are even more coordinating than aHF and for that reason not suitable for growing of the single crystals of M (XF 6 ) 2 compounds [3]. The decomposed surface layer made of M (XF 6 ) 2 phases can sometimes prevent or slow down the complete decomposition of HF-rich M(HF) n (XF 6 ) 2 phases [28].…”